Preparation of cross-linked nanoporous poly(ethylene glycol) diacrylate membrane in hexagonal lyotropic liquid crystal phases

Cross-linked poly(ethylene glycol) diacrylate (PEGDA) membranes were prepared by polymerization in periodic nanostructured lyotropic liquid crystals (LLC) hexagonal phases under UV light. A series of membranes were prepared under different purification treatment conditions. Polarized light microscope was employed to determine the LLC phase texture of LLC system before and after polymerization. It is found that the LLC hexagonal structure retained to some degree after polymerization. The interior structures of final membranes were investigated with scanning electron microscope (SEM). The results suggested that purification process affect the structure retention.

Structure retention in cross-linked poly(ethylene glycol) diacrylate hydrogel templated from a hexagonal lyotropic liquid crystal by controlling the surface tension

Retaining hexagonal lyotropic liquid crystal (LLC) structures in polymers after surfactant removal and drying is particularly challenging, as the surface tension existing during the drying processes tends to change the morphology. In this study, cross-linked poly(ethylene glycol) diacrylate (PEGDA) hydrogels were prepared in LLC hexagonal phases formed from a dodecyltrimethylammonium bromide (DTAB)/water system. The retention of the hexagonal LLC structures was examined by controlling the surface tension. Polarized light microscopy, X-ray diffraction and small angle X-ray scattering results indicate that the hexagonal LLC structure was successfully formed before polymerization and well retained after polymerization and after surfactant removal when the surface tension forces remained neutral. Controlling the surface tension during the drying process can retain the nanostructures templated from lyotropic liquid crystals which will result in the formation of materials with desired nanostructures.

Retention of the original LLC structure in a cross-linked poly(ethylene glycol) diacrylate hydrogel with reinforcement from a silica network

Cross-linked poly(ethylene glycol) diacrylate (PEGDA) hydrogels with uniformly controlled nanoporous structures templated from hexagonal lyotropic liquid crystals (LLC) represent separation membrane materials with potentially high permeability and selectivity due to their high pore density and narrow pore size distribution. However, retaining LLC templated nanostructures is a challenge as the polymer gels are not strong enough to sustain the surface tension during the drying process. In the current study, cross-linked PEGDA gels were reinforced with a silica network synthesized via an in situ sol-gel method, which assists in the retention of the hexagonal LLC structure. The silica precursor does not obstruct the formation of hexagonal phases. After surfactant removal and drying, these hexagonal structures in samples with a certain amount of tetraethoxysilane (TEOS) loading are well retained while the nanostructures are collapsed in samples without silica reinforcement, leading to the hypothesis that the reinforcement provided by the silica network stabilizes the LLC structure. The study examines the conditions necessary for a sufficient and well dispersed silica network in PEGDA gels that contributes to the retention of original LLC structures, which potentially enables broad applications of these gels as biomedical and membrane materials.

Nano-capsules of amphiphilic poly (ethylene glycol)-block-poly (bisphenol A carbonate) copolymers via thermodynamic entrapment

The synthesis of amphiphilic poly(ethylene glycol)-block-poly(bisphenol A carbonate) (PEG-b-PC) block copolymer is presented here using a simple bio-chemistry coupling reaction between poly(bisphenol A carbonate) (PC) with a monomethylether poly(ethylene glycol) (mPEG-OH) block, mediated by dicyclohexylcarbodiimide/4-dimethylaminopyridine. This method inherently allows great flexibility in the choice of starting materials as well as easy product purification only requiring phase separation and water washing. Collective data from Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and modulated dynamic scanning calorimetry (MDSC) confirmed the successful attachment of the poly(ethylene glycol) (mPEG-OH) and poly(bisphenol A carbonate) (PC) blocks. The preparation of nano-capsules was carried out by sudden addition of water to PEG-b-PC copolymers dispersed in THF, resulting in the controlled precipitation (i.e. thermodynamic entrapment) of the copolymer. Nano-capsules as small as 85 nm ± 30 nm were produced using this simple and fast methodology. We also demonstrate that encapsulating a water-insoluble bisphenol A diglycidyl ether (DGEBA) epoxy resin is possible highlighting the potential use of these capsules as a chemical delivery system.

Synthesis and self-assembly behaviour of poly(Nα-Boc-l-tryptophan)-block-poly(ethylene glycol)-block-poly(Nα-Boc-l-tryptophan)

We report for the first time the use of Nα-Boc-l-tryptophan for the synthesis of amphiphilic BAB triblock copolymers for potential drug delivery applications. A library of poly(Nα-Boc-l-tryptophan)-block-poly(ethylene glycol)-block-poly(Nα-Boc-l-tryptophan) (PBoclTrp-b-PEG-b-PBoclTrp) amphiphilic copolymers were synthesized through the ring opening polymerization of Nα-Boc-l-tryptophan Nα-carboxy anhydride as initiated by diamino-terminated PEG of fixed molecular weight (Mn 3350). The influence of the hydrophobic block length over self-assembly was investigated for 4 of the BAB copolymers of molecular weights varying between Mn 5000 and Mn 17000. It was found that an increase in hydrophobic block length led to an increase in hydrodynamic size of aggregates in solution, as well as a decrease in critical micelle concentration. TEM analysis showed the formation of spherical micelles with the largest of the copolymers forming interconnected networks of spherical micelles. The influence of hydrophobic block length over the formation of secondary structure was analyzed using circular dichroism and infrared spectroscopy. Collectively we found that the presence of t-Boc protected l-tryptophan leads to the preferential formation of α-helix secondary structure through hydrogen bonding, which, in a drug delivery vehicle context, could help in controlling drug release. Also, it is believed that the use of novel Nα-Boc-l-tryptophan could improve drug stabilization in the hydrophobic core via π-π interactions between indole rings.